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Acid-Base Interactions at the Molecular Level: Adhesion and Friction Studies with Interfacial Force Microscopy

Description: To examine the forces of acid-base adhesive interactions at the molecular level, we utilize the scanning probe Interracial Force Microscope (IFM). Unlike cantilever-based atomic force microscopes, the EM is a non-compliant, mechanically stable probe that provides a complete adhesive profile without jump-to-contact. In this way, we are able to quantitatively measure the work of adhesion and bond energies at well-defined, nanometer-scale single asperity contacts. In particular, we will discuss the displacement-controlled adhesive forces between self-assembled monolayer of functionalized alkanethiols strongly bound to a gold substrate and a similarly functionalized tip. We also discuss a method utilizing decoupled lateral and normal force sensors to simultaneously observe the onset of both friction and chemical bond formation. Measurements show that friction can be directly attributed to bond formation and rupture well before repulsive contact.
Date: December 9, 1998
Creator: Burns, A.R.; Carpick, R.W.; Houston, J.E. & Michalske, T.A.
Partner: UNT Libraries Government Documents Department

Wetting of a Chemically Heterogeneous Surface

Description: Theories for inhomogeneous fluids have focused in recent years on wetting, capillary conden- sation, and solvation forces for model systems where the surface(s) is(are) smooth homogeneous parallel plates, cylinders, or spherical drops. Unfortunately natural systems are more likely to be hetaogeneous both in surt%ce shape and surface chemistry. In this paper we discuss the conse- quences of chemical heterogeneity on wetting. Specifically, a 2-dimensional implementation of a nonlocal density functional theory is solved for a striped surface model. Both the strength and range of the heterogeneity are varied. Contact angles are calculated, and phase transitions (both the wetting transition and a local layering transition) are located. The wetting properties of the surface ase shown to be strongly dependent on the nature of the surface heterogeneity. In addition highly ordered nanoscopic phases are found, and the operational limits for formation of ordered or crystalline phases of nanoscopic extent are discussed.
Date: November 20, 1998
Creator: Frink, L.J.D. & Salinger, A.G.
Partner: UNT Libraries Government Documents Department

Reconstruction of surfaces in NiO

Description: We studied the reconstructions of surfaces in NiO by atomistic simulations which utilize Buckingham short range potentials and the shell model. It was found that (hk0) surfaces prefer to reconstruct into (100) surface facets which has the lowest energy. The interaction between these (100) facets is repulsive and converges to zero as size of facets grows. The (111) surface can be stabilized by reconstruction into (100) micro-facets.
Date: July 1, 1995
Creator: Yan, M. & Chen, S.P.
Partner: UNT Libraries Government Documents Department

Surface Modified Coals for Enhanced Catalyst Dispersion and Liquefaction

Description: The aim of this study is to enhance catalyst loading and dispersion in coal for improved liquefaction by preadsorption of surfactants and catalysts on to the coal. During this reporting period, the effects of dodecyl dimethyl ethyl ammonium bromide (DDAB) (a cationic surfactant), sodium dodecyl sulfate (SDS) (an anionic surfactant), Triton X-100 (a neutral surfactant), and ferrous sulfate (as a catalyst precursor) on the coal surface charge at various pH values were determined. The results of the zeta potential measurements suggest that ferrous sulfate as catalyst precursor creates a distinctly different condition on the coal surface compared to that of molybdenum as reported in the previous progress reports. The effects of the adsorption of the surfactants also varied distinctly with the type of surfactant. With the adsorption of DDAB, the cationic surfactant, the surface charge was more positive. The opposite effect was observed for the SDS, the anionic surfactant. The coals treated with Triton X-100, the neutral surfactant, also showed an overall negative surface charge density. The adsorption of the catalyst precursor (ferrous sulfate) resulted in a net negative charge on the coal surface.
Date: December 4, 1998
Creator: Yeboah, Yaw D.
Partner: UNT Libraries Government Documents Department

Optimizing fabrication of electrodeposited 3D surface features

Description: Selective electrodeposition onto specially masked surfaces (producing blind holes with non-conductive side walls) has been investigated. The thick masks are low cost polymer sheet into which holes and other patterns are machined. Plating with this type of masking system is one method of fabricating medium aspect ratio metallic structures (structures whose width to length ratio is greater than 10/1). The experiment was conducted with deposits of OFC copper from an acid sulfate solution, but similar results are expected with other metals. Structure diameter varied from 0.25 mm to 3.8 mm (0.01`` to 0.150``). The effect of current density, electrolyte concentration, solution temperature, and agitation on deposition rate were investigated. Deposit quality, deposition rate, and optimal plating parameters were evaluated.
Date: July 1, 1998
Creator: Steffani, C., LLNL
Partner: UNT Libraries Government Documents Department

Nonlinear optical studies of surfaces

Description: The possibly of using nonlinear optical processes for surface studies has attracted increasing attention in recent years. Optical second harmonic generation (SHG) and sum frequency generation (SFG), in particular, have been well accepted as viable surface probes. They have many advantages over the conventional techniques. By nature, they are highly surface-specific and has a submonolayer sensitivity. As coherent optical processes, they are capable of in-situ probing of surfaces in hostile environment as well as applicable to all interfaces accessible by light. With ultrafast pump laser pulses, they can be employed to study surface dynamic processes with a subpicosecond time resolution. These advantages have opened the door to many exciting research opportunities in surface science and technology. This paper gives a brief overview of this fast-growing new area of research. Optical SHG from a surface was first studied theoretically and experimentally in the sixties. Even the submonolayer surface sensitivity of the process was noticed fairly early. The success was, however, limited because of difficulties in controlling the experimental conditions. It was not until the early 1980`s that the potential of the process for surface analysis was duly recognized. The first surface study by SHG was actually motivated by the then active search for an understanding of the intriguing surface enhanced Raman scattering (SERS). It had been suspected that the enhancement in SERS mainly came from the local-field enhancement due to local plasmon resonances and pointing rod effect on rough metal surfaces. In our view, Raman scattering is a two-photon process and is therefore a nonlinear optical effect.
Date: July 1, 1994
Creator: Shen, Y.R.
Partner: UNT Libraries Government Documents Department

Spontaneous Pattern Formation on Ion Bombarded Si(001)

Description: Pattern formation on surfaces undergoing low-energy ion bombardment is a common phenomenon. Here, a recently developed in situ spectroscopic light scattering technique was used to monitor periodic ripple evolution on Si(001) during Ar(+) sputtering. Analysis of the rippling kinetics indicated that under high flux sputtering at low temperatures the concentration of mobile species on the surface is saturated, and, surprisingly, is both temperature and ion flux independent. This is due to an effect of ion collision cascades on the concentration of mobile species. This new understanding of surface dynamics during sputtering allowed us to measure straighforwardly the activation energy for atomic migration on the surface to be 1.2+0.1 eV. The technique is generalizable to any material, including high temperature and insulating materials for which surface migration energies are notoriously difficult to measure.
Date: April 26, 1999
Creator: Chason, Eric; Erlebacher, Jonah, Aziz, Michael J.; Floro, Jerrold A. & Sinclair, Michael B.
Partner: UNT Libraries Government Documents Department

Lectures on geometrical properties of nuclei

Description: Material concerning the geometrical properties of nuclei is drawn from a number of different sources. The leptodermous nature of nuclear density distributions and potential wells is used to draw together the various geometrical properties of these systems and to provide a unified means for their description. Extensive use is made of expansions of radial properties in terms of the surface diffuseness. A strong case is made for the use of convolution as a geometrical ansatz for generating diffuse surface distributions because of the number of simplifications that arise which are of practical importance. 7 figures. (auth)
Date: November 1, 1975
Creator: Myers, W.D.
Partner: UNT Libraries Government Documents Department

LDRD final report : on the development of hybrid level-set/particle methods for modeling surface evolution during feature-scale etching and deposition processes.

Description: Two methods for creating a hybrid level-set (LS)/particle method for modeling surface evolution during feature-scale etching and deposition processes are developed and tested. The first method supplements the LS method by introducing Lagrangian marker points in regions of high curvature. Once both the particle set and the LS function are advanced in time, minimization of certain objective functions adjusts the LS function so that its zero contour is in closer alignment with the particle locations. It was found that the objective-minimization problem was unexpectedly difficult to solve, and even when a solution could be found, the acquisition of it proved more costly than simply expanding the basis set of the LS function. The second method explored is a novel explicit marker-particle method that we have named the grid point particle (GPP) approach. Although not a LS method, the GPP approach has strong procedural similarities to certain aspects of the LS approach. A key aspect of the method is a surface rediscretization procedure--applied at each time step and based on a global background mesh--that maintains a representation of the surface while naturally adding and subtracting surface discretization points as the surface evolves in time. This method was coded in 2-D, and tested on a variety of surface evolution problems by using it in the ChISELS computer code. Results shown for 2-D problems illustrate the effectiveness of the method and highlight some notable advantages in accuracy over the LS method. Generalizing the method to 3D is discussed but not implemented.
Date: January 1, 2005
Creator: McBride, Cory L. (Elemental Technologies, American Fork, UT); Schmidt, Rodney Cannon & Musson, Lawrence Cale
Partner: UNT Libraries Government Documents Department

Dynamic response of physisorbed hydrogen molecules on lanthanide-modified zirconia nanoparticles

Description: We investigated the microstructure and surface properties of ultrafine Ce- and Nd-modified zirconia powders by a joint adsorption-isotherm and neutron-scattering study. While the average pore size distribution and specific surface area can be determined by BET analysis of nitrogen adsorption, neutron inelastic scattering from surface adsorbed hydrogen provides additional information about the modulation of local potential energies over the substrate surfaces and distinguishes subtle differences in the microporous and mesoporous structure of the two samples.
Date: December 31, 1996
Creator: Loong, C.K.; Trouw; Ozawa, Masakuni & Suzuke, Suguru
Partner: UNT Libraries Government Documents Department

Final technical report on Award No. DE-FG02-92ER45465

Description: The motivation of the previous program was to develop methods which could be used in a systematic study of the interface between glass and crystalline oxides. It was recognized that since the mechanical properties of glass-containing oxides are particularly important, it would be desirable to have a method which would also allow a systematic comparison of the mechanical properties of the materials. We found that the geometry of a glass film on a crystalline surface gave several new possibilities: we could develop methods for examining the mechanical properties of the films and the interfaces and we could examine both the crystallization of glass films and their wetting/dewetting behavior. Also, the samples are amenable to examination by the characterization techniques which give information on the chemistry and structure over a wide range of length scales: both chemistry and crystallography can be controlled and changes monitored.
Date: June 18, 2003
Creator: Carter, C. Barry
Partner: UNT Libraries Government Documents Department

RHEED studies of Ag/Si(111) growth at low temperatures

Description: This thesis showed that it is possible to achieve well ordered growth at low temperatures when chaing fluxes during the course of the deposition. It was also demonstrated that nucleation theory fails to predict or explain at least part of the results, in particular when deposition takes place at an initially low rate, with presumably a relatively low nucleation density, followed by a change to a high flux rate. This points to an inherent lack of nucleation theory; alternative explanations are presented based on flux-independent growth as reported by Roos (Surf. Sci. 302 (1994) 37).
Date: January 2, 1996
Creator: Koehler, U.
Partner: UNT Libraries Government Documents Department

Surface properties of photo-oxidized bituminous coals. Technical progress report, April 1995--June 1995

Description: During this report period, analysis of the vitrinite concentrate samples of the Lower Kittanning (PSOC-1562) and Illinois No. 6 (DECS-24) seams were completed. These results show that the concentrates are in excess of 97 vol. % vitrinite and that the sample remains in good shape for microflotation and GC/MS experiments. Two new coal samples, the hvAb Banner seam (DECS-29) and the mvb Splashdam seam (DECS-30) were collected in mid-June. Preliminary processing of the channel samples suggests that the Banner seam sample is severely weathered and may need to be replaced. Collection of a third sample, the hvBb Ohio No. 4a seam, was delayed until next quarter. Surface oxidation of a powdered vitrinite concentrate sample of the Pittsburgh seam (DECS-23) was completed during this quarter. The technique of photo-oxidizing vitrain samples using our optical microscope was laborious and time consuming. Even after the procedure was streamlined the procedure of irradiating 1.4 g of vitrinite required 29 days. A limited number of samples will be irradiated in this manner in order to maintain continuity between our fluorometric measurements and microflotation experiments, but other methods of surface oxidation will be explored. Presentations were made at the DOE Contractor`s Review and Peer Review meetings held in Nashville, TN on June 13-14, 1995.
Date: August 1, 1995
Creator: Mitchell, G.; Davis, A. & Chander, S.
Partner: UNT Libraries Government Documents Department

The influence of surface topography on the forming friction of automotive aluminum sheet

Description: Interest in utilizing aluminum alloys in automobiles has increased in recent years as a result of the desire to lower automobile weight and, consequently, increase fuel economy. While aluminum alloy use in cast parts has increased, outer body panel applications are still being investigated. The industry is interested in improving the formability of these sheet alloys by a combination of alloy design and processing. A different avenue of improving the formability of these alloys may be through patterning of the sheet surface. Surface patterns hold the lubricant during the forming process, with a resulting decrease in the sheet-die surface contact. While it has been speculated that an optimum surface pattern would consist of discrete cavities, detailed investigation into the reduction of forming friction by utilizing discrete patterns is lacking. A series of discrete patterns were investigated to determine the dependence of the forming friction of automotive aluminum alloys on pattern lubricant carrying capacity and on material strength. Automotive aluminum alloys used in outer body panel applications were rolled on experimental rolls that had been prepared with a variety of discrete patterns. All patterns for each alloy were characterized before and after testing both optically and, to determine pattern lubricant capacity, using three dimensional laser profilometry. A draw bead simulation (DBS) friction tester was designed and fabricated to determine the forming friction of the patterned sheets. Tensile testing and frictionless DBS testing were performed to ascertain the material properties of each sheet. The most striking result of this work was the inversely linear dependence of forming friction on the lubricant carrying capacity of the discrete patterns.
Date: May 1, 1998
Creator: Kramer, P.A.
Partner: UNT Libraries Government Documents Department

Diffuse reflectance FTIR of stains on grit blasted metals

Description: Diffuse reflectance mid-infrared Fourier transform (DRIFT) spectroscopy has been applied to the detection of oil contamination on grit-blasted metals. The object of this application is to detect and discriminate between silicone and hydrocarbon oil contamination at levels approaching 10 mg/m{sup 2}. A portable FTIR spectrometer with dedicated diffuse reflectance optics was developed for this purpose. Using translation devices positioned by instructions from the spectrometer operating system, images of macroscopic substrates were produced with millimeter spatial resolution. The pixels that comprise an image are each a full mid-infrared spectrum with excellent signal-to-noise, each determined as individual files and uniquely saved to disc. Reduced spectra amplitudes, based on peak height, area, or other chemometric techniques, mapped as a function of the spatial coordinates of the pixel are used to display the image. This paper demonstrates the application of the technique to the analysis of stains on grit-blasted metals, including the calibration of the method, the inspection of substrates, and the migration of oil contamination.
Date: August 9, 1997
Creator: Powell, G.L.; Hallman, R.L. Jr. & Cox, R.L.
Partner: UNT Libraries Government Documents Department

Silicon crystal surface temperature: Computational and radiometric studies

Description: The surface temperature of the three-channel, gallium cooled Cornell silicon crystal was evaluated for the given system configuration and specifications. The THTB thermal-hydraulic program is used for the numerical solution of the problem, and the results are to be compared with the radiometric measurements obtained at Cornell.
Date: December 1, 1988
Creator: Khounsary, A.M.; Kuzay, T.M. & Forster, G.A.
Partner: UNT Libraries Government Documents Department

Electric Field Induced Surface Modification of Au

Description: We discuss the role of localized high electric fields in the modification of Au surfaces with a W probe using the Interfacial Force Microscope. Upon bringing a probe close to a Au surface, we measure both the interfacial force and the field emission current as a function of separation with a constant potential of 100 V between tip and sample. The current initially increases exponentially as the separation decreases. However, at a distance of less than {approximately} 500{angstrom} the current rises sharply as the surface begins to distort and rapidly close the gap. Retraction of the tip before contact is made reveals the formation of a mound on the surface. We propose a simple model, in which the localized high electric field under the tip assists the production of mobile Au adatoms by detachment from surface steps, and a radial field gradient causes a net flux of atoms toward the tip by surface diffusion. These processes give rise to an unstable surface deformation which, if left unchecked, results in a destructive mechanical contact. We discuss our findings with respect to earlier work using voltage pulses in the STM as a means of nanofabrication.
Date: February 15, 1999
Creator: Erchak, A. A.; Franklin, G. F.; Houston, J. E.; Mayer, T. M. & Michalske, T. A.
Partner: UNT Libraries Government Documents Department

Cesium/oxide interactions for ultrathin films on {alpha}-Al{sub 2}O{sub 3}(0001) and {alpha}-Al{sub 2}O{sub 3}(1{bar 1}02)

Description: The interaction of cesium at the (0001) and (1{bar 1}02) surfaces of sapphire has been investigated using a variety of surface analytical techniques. Reflection mass spectrometric measurements yield initial Cs adsorption probabilities of 0.9 and 0.85 for the unreconstructed (0001) and (1{bar 1}02) surfaces, respectively. The adsorption probability decreases dramatically for these surfaces at critical Cs coverages of 2.O {times} 10{sup 14} and 3.4 {times} 10{sup 14} atoms/cm{sup 2}, respectively. Thermally induced reconstruction of the (0001) surface to form an oxygen deficient surface results in a decrease in the initial probability and capacity for Cs adsorption. Low energy electron diffraction (LEED) demonstrates that an intermediate, mixed domain surface yields an initial adsorption probability of 0.5 while a ({radical}31 {times} {radical}31) R {plus_minus} 9{degree} reconstructed surface yields a value of 0.27. Thermal desorption mass spectrometry (TDMS) shows that surface reconstruction eliminates the high binding energy states of Cs (2.7 eV/atom), consistent with the observed changes in adsorption probability. In contrast, reconstruction of the (1{bar 1}02) surface produces only minor changes in Cs adsorption. X-ray photoelectron spectroscopy (XPS) indicates that no formal reductive/oxidative chemistry takes place at the interface. We interpret the facile adsorption and strong binding of Cs on sapphire to result from Cs interacting with coordinatively unsaturated oxygen.
Date: March 1, 1995
Creator: Zavadil, K.R. & Ing, J.L.
Partner: UNT Libraries Government Documents Department

HRLEED study of the roughening transitions in Cu(110), Ni(110) and Ag(110) surfaces

Description: The authors present the results of High Resolution Low Energy Electron Diffraction (HRLEED) measurements of the thermal roughening transition on Cu(110), Ag(110) and Ni(110) surfaces. They performed careful spot profile intensity measurements as a function of temperature. They observed a proliferation of steps along the (110) and (001) directions. In addition a strong deviation from a Debye model was observed in the scattered intensity of the Bragg reflections. This deviation from the harmonic approximation occurs well below the roughening transition temperature. The behavior of the three metal surfaces is qualitatively similar except for the transition temperatures. Ni shows the highest transition temperature (1,300 K), Cu is intermediate (1,000 K) and Ag has the lowest temperature (730 K). Analyzing the behavior of the (00) reflection intensity, and the evolution of the line shape as a function of the temperature, they found clear evidence of a roughening transition at the (110) surface. A lineshape analysis of the (00) reflection shows the transition from a Lorentzian lineshape to a power law. They also proved, based on the experimental data and a recent theoretical model, that there is a tremendous increase in step density and a decrease in the average terrace size as the temperature increases. They used STM to corroborate the HRLEED results at room temperature. They found excellent agreement.
Date: December 1, 1996
Creator: Wang, K. & Montano, P.A.
Partner: UNT Libraries Government Documents Department

Cutting fluid study for single crystal silicon

Description: An empirical study was conducted to evaluate cutting fluids for Single Point Diamond Turning (SPDT) of single crystal silicon. The pH of distilled waster was adjusted with various additives the examine the effect of pH on cutting operations. Fluids which seemed to promote ductile cutting appeared to increase tool wear as well, an undesirable tradeoff. High Ph sodium hydroxide solutions showed promise for further research, as they yielded the best combination of reduced tool wear and good surface finish in the ductile regime. Negative rake tools were verified to improve the surface finish, but the negative rake tools used in the experiments also showed much higher wear than conventional 0{degree} rake tools. Effects of crystallographic orientation on SPDT, such as star patterns of fracture damage forming near the center of the samples, were observed to decrease with lower feedrates. Silicon chips were observed and photographed, indicative of a ductile materials removal process.
Date: May 5, 1998
Creator: Chargin, D.
Partner: UNT Libraries Government Documents Department

Thickness dependencies in the calculated properties of metallic ultra-thin films

Description: Ultra-thin film (UTF) electronic structure calculations are a common tool for investigating surface properties. For this approximation to be useful, the UTF must be thick enough that the surfaces are decoupled and the interior is bulk-like, yet thin enough that a high precision electronic structure calculation is affordable. These conditions can only be satisfied simultaneously if the properties of interest converge rapidly as the UTF thickness is increased. In this work, electronic structure calculations for Al(111) films ranging from one to twelve atoms thick are used to illustrate some of the difficulties that can arise when one attempts to determine surface properties of metals with UTF calculations.
Date: December 1, 1997
Creator: Boettger, J.C.
Partner: UNT Libraries Government Documents Department